EP1270199A1 - Mehrschichtiges laminat, harstellungs- und formgebungsverfahren - Google Patents

Mehrschichtiges laminat, harstellungs- und formgebungsverfahren Download PDF

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Publication number
EP1270199A1
EP1270199A1 EP00905391A EP00905391A EP1270199A1 EP 1270199 A1 EP1270199 A1 EP 1270199A1 EP 00905391 A EP00905391 A EP 00905391A EP 00905391 A EP00905391 A EP 00905391A EP 1270199 A1 EP1270199 A1 EP 1270199A1
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EP
European Patent Office
Prior art keywords
sheet
thermoplastic resin
layer
fibers
layer sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP00905391A
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English (en)
French (fr)
Other versions
EP1270199A4 (de
Inventor
Kazuo c/o Sekisui Kagaku Kogyo K.K YAMAGATA
Isao c/o Sekisui Kagaku Kogyo K. K HIGUCHI
Takamasa c/o Sekisui Kagaku Kogyo K.K. FUKUOKA
Michitaka c/o Sekisui Kagaku Kogyo KK TSUJIMOTO
Masashi c/o Sekisui Kagaku Kogyo K.K OKABE
Yoshihiro c/o Sekisui Kagaku Kogyo K. K. INUI
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Publication date
Application filed by Sekisui Chemical Co Ltd filed Critical Sekisui Chemical Co Ltd
Publication of EP1270199A1 publication Critical patent/EP1270199A1/de
Publication of EP1270199A4 publication Critical patent/EP1270199A4/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
    • B29C44/1209—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements by impregnating a preformed part, e.g. a porous lining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/35—Component parts; Details or accessories
    • B29C44/352—Means for giving the foam different characteristics in different directions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/05—5 or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249955—Void-containing component partially impregnated with adjacent component
    • Y10T428/249958—Void-containing component is synthetic resin or natural rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/24996—With internal element bridging layers, nonplanar interface between layers, or intermediate layer of commingled adjacent foam layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • Y10T428/249992—Linear or thermoplastic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y10T428/249987—With nonvoid component of specified composition
    • Y10T428/249991—Synthetic resin or natural rubbers
    • Y10T428/249992—Linear or thermoplastic
    • Y10T428/249993—Hydrocarbon polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/647—Including a foamed layer or component

Definitions

  • the present invention relates to a multi-layer sheet, which is excellent in lightweight property, bending strength, compressive strength, thermoforming property and dimensional stability, to a manufacturing method of the multi-layer sheet and to a molding method thereof.
  • foam made of thermoplastic resin is used as an insulation material, a buffer material, and a floating material, since the foam is excellent in lightweight property, insulation property and flexibility.
  • polyolefin-based resin foam in particular, is widely used for such upholstery materials as doors, ceilings, instrument panels etc. of vehicles by secondary thermoforming, as the polyolefin-based resin foam is excellent in heat-resisting property, dimensional stability, and so on.
  • thermoplastic resin foam containing polyolefin-based resin foam is used.
  • accessories of the vehicle such as a lamp were conventionally mounted to an upholstery material after the upholstery material was installed in the vehicle.
  • a module system in assembling vehicles has advanced these years, in which the accessories such as the lamp are mounted to the upholstery material of the vehicle in advance, and the upholstery material provided with the accessories is installed in the vehicle. Accordingly, better bending strength and better compression rigidity are required than before for a use for the upholstery material.
  • a purpose of the present invention is to provide a multi-layer sheet, which is excellent in bending strength, compressive strength, a thermoforming property and dimensional stability as well as a lightweight property, and to provide a manufacturing method of the multi-layer sheet and a molding method thereof.
  • the multi-layer sheet according to the present invention comprises a thermoplastic resin foam sheet and a reinforcing sheet layered on and integrated with at least one side of the thermoplastic resin foam sheet, in which the reinforcing sheet comprises non-woven fabric where non-meltable fibers are interwound with one another and are bound together with a thermoplastic resin, and in which bubbles of the thermoplastic resin foam sheet have an aspect ratio Dz/Dxy of 1.2 or more, and an expansion ratio of 5 ⁇ 50cc/g.
  • thermoplastic resin used for the above-mentioned thermoplastic resin foam sheet is not limited as long as the thermoplastic resin is the one, which has been conventionally and usually used to provide foam.
  • polyolefin-based resins such as polyethylenes like low density polyethylene, straight-chain low density polyethylene, medium density polyethylene, high density polyethylene and so on, polypropylenes like isotactic polypropylene, syndiotactic polypropylene and so on, polybutene, ethylene- ⁇ -olefin copolymer and so on; ethylene-propylene-diene terpolymer; ethylene-vinyl acetate copolymer; ethylene-acrylic ester copolymer; polystyrene-based resins such as polystyrene, polystyrene-based thermoplastic resin elastomer and so on may be enumerated.
  • polyolefin-based resins are preferable, polyethylene and polypropylene are more preferable, and a mixture of polyethylene and polypropylene is particularly preferable in terms of superiority in lightweight property, chemical resistance, flexibility and elasticity of the obtained multi-layer sheet.
  • thermoplastic resins may be used independently or jointly. In case polyolefin-based resin and the other thermoplastic resins are used jointly, it is preferable to regulate the polyolefin-based resins to be 70 weight % or more of a total amount of resins.
  • thermoplastic resins are foamed by using pyrolysis-type foaming agent in a manner as described hereinafter, it is necessary to provide fluidity by melting the thermoplastic resins, however, as a melting point of the thermoplastic resins except polyolefin-based resins is generally higher than that of the polyolefin-based resins, if a content of the polyolefin-based resins is small, the melting point of the whole thermoplastic resin becomes high, and at a time of foaming, the fluidity of the whole thermoplastic resin becomes low, consequence of which is that foaming performance may be spoiled.
  • ⁇ -olefin propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, and so on are enumerated, and as copolymers containing an ethylene component, any one of a block copolymer, a random copolymer and a random block copolymer may be used.
  • polyolefin-based resins added with a polystyrene-based resins are preferable to obtain the multi-layer sheet, which is superior in lightweight property, chemical resistance, flexibility, high elasticity and mechanical strength.
  • preferable content of the polystyrene-based resins is 30 weight % or less of the total amount of the polyolefin-based resins and the polystyrene-based resins.
  • thermoplastic resin is required to have elongation stress to a predetermined extent at the time of foaming
  • a crosslinking structure is provided in methods as described below, for example.
  • thermoplastic resin foam sheet which is superior in lightweight and recycling properties provided with a required range of fluidity and elongation stress at the time of foaming, is as follows. Namely, the above-mentioned thermoplastic resin and a multifunctional monomer, which has two multifunctional groups or more being able to carry out a radical reaction, is supplied to a generally-used melting and kneading extruder after organic peroxide is added according to necessity.
  • thermoplastic resin is allowed to be reacted with the multifunctional monomer in the melting and kneading extruder to provide a modified thermoplastic resin.
  • the thermoplastic resin is allowed to be reacted with the multifunctional monomer, and a part of the crosslinking structure, which is intended to be finally given to the thermoplastic resin, is introduced to the thermoplastic resin.
  • the modified thermoplastic resin is formed to be a required form such as a form of a sheet and so on.
  • the crosslinking structure is further given to the thermoplastic resin by heating the modified thermoplastic resin to a temperature higher than a reaction temperature of the multifunctional monomer in order to provide elongation stress, which is suitable for foaming.
  • Modification of the thermoplastic resin by having the multifunctional monomer reacted with the above-mentioned thermoplastic resin can be carried out in a manner that the organic peroxide is added to the thermoplastic resin and the multifunctional monomer, according to necessity requires, which is then supplied to the generally-used melting and kneading extruder in order to be melted and kneaded.
  • the organic peroxide is added to the thermoplastic resin and the multifunctional monomer, according to necessity requires, which is then supplied to the generally-used melting and kneading extruder in order to be melted and kneaded.
  • a divinyl compound or a diallyl compound is used in particular as the above-mentioned multifunctional monomer, addition of the organic peroxide is preferable.
  • the multifunctional monomer a dioxime compound, a bismaleimide compound, a divinyl compound, an allylic multifunctional compound, a (metha) acrylic multifunctional compound, a quinone compound, and so on are enumerated.
  • the above-mentioned dioxime compound means a compound which has two oxime groups indicated by a chemical formula ( I ) or two substituted oxime groups indicated by a chemical formula (II) in which a hydrogen atom in the oxime group is substituted with another atomic group R (mainly hydrocarbon group), or a compound which has both of the aforementioned one oxime group and the one substituted oxime group.
  • p,p'-dibenzoyl quinone dioxime indicated by a chemical formula (VI) and so on are enumerated.
  • the dioxime compounds may be used independently or jointly.
  • the above-mentioned bismaleimide compound means a compound which has two or more structures of maleic acid imide (maleimide) indicated by a chemical formula ( V ) in a molecule thereof.
  • maleimide maleic acid imide
  • V chemical formula
  • N, N'-m-phenylene bismaleimide indicated by a chemical formula (VII) diphenylmethane bismaleimide indicated by a chemical formula (VIII) and so forth are enumerated.
  • polymaleimide which has two or more maleimide structures as indicated by a chemical formula (IX) in a molecule thereof, is also included in the bismaleimide compound.
  • diallyl phthalate as indicated by a chemical formula (X I )
  • triallyl cyanulate as indicated by a chemical formula (X II)
  • triallyl isocyanulate as indicated by a chemical formula (X III)
  • diallyl chlorendate as indicated by a chemical formula (X IV) and so forth are enumerated.
  • di(metha)acrylic compounds as alkandiol di(metha) acrylate, ethylene glycol di(metha) acrylate, propylene glycol di(metha)acrylate, polyethylene glycol di(metha) acrylate, polypropylene grycol di(metha) acrylate, neopentyl glycol di(metha) acrylate, dimethylol tricyclodecane di(metha)acrylate, ethylene glycol adduct di(metha) acrylate of bisphenol A, propylene glycol adduct di(metha)acrylate of bisphenol A and so on, such tri(metha)acrylic compounds as trimethylol propane tri(metha) acrylate, pentaerythritol tri(metha) acrylate, trimethylolpropane ethylene oxide adduct tri(metha) acrylate, glycerol propylene oxide ad
  • the amount of addition of the above-mentioned multifunctional monomers should preferably be 0.05 ⁇ 5 weight parts, or more preferably be 0.2 ⁇ 2 weight parts to 100 weight parts of the thermoplastic resin.
  • thermoplastic resin may be decomposed. If the temperature is low, modification of the thermoplastic resin is carried out insufficiently, the elongation stress of the expandable sheet at a time of foaming becomes insufficient, and a thermoplastic resin foam sheet with a required expansion ratio may not be able to be obtained. Therefore, the temperature should preferably be 170 ° C or higher and be a decomposition temperature of the thermoplastic resin or lower, and more preferably be 200 ⁇ 250 ° C.
  • thermoplastic resin foam sheet with spindle-shaped bubbles having the aspect ratio within a required range which will be described hereinafter
  • the modified thermoplastic resin which is further added with the unmodified thermoplastic resin is melted and kneaded.
  • the above-mentioned modified thermoplastic resin and the unmodified thermoplastic resin may be of the same kind or of the different kind as far as these two resins are compatible with each other.
  • organic peroxide is not particularly limited as far as it is possible to have the multifunctional monomer reacted with the thermoplastic resin.
  • dicumyl peroxide 2,5-dimethyl-2,5-di(t-butyl peroxy) hexane, 2,5-dimethyl-2,5-di(t-butyl peroxy)-3-hexyne are preferable.
  • the above-mentioned organic peroxides may be used independently or jointly.
  • the amount should preferably be 0.001 ⁇ 0.5 weight parts or should more preferably be 0.005 ⁇ 0.15 weight parts to 100 weight parts of the thermoplastic resin.
  • thermoplastic resin with the crosslinking structure is that a predetermined amount of ionizable radiation is applied to the thermoplastic resin after a predetermined amount of crosslinking agent is added to the thermoplastic resin.
  • crosslinking agent is not particularly limited as far as the crosslinking agent is what is generally used for crosslinking of thermoplastic resins.
  • the crosslinking agent is what is generally used for crosslinking of thermoplastic resins.
  • o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, trimythylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, trimelliticacidtriallyl ester, triallylisocyanurate, etc. are enumerated.
  • the crosslinking agents may be used independently or jointly.
  • the amount should preferably be 0.1 ⁇ 10 weight parts or should more preferably be 0.3 ⁇ 5 weight parts to 100 weight parts of the thermoplastic resin.
  • Degree of crosslinking by the above-mentioned ionizable radiation is regulated by using gel fraction as a criterion. If the gel fraction is large, moldability of the multi-layer sheet may be lowered, and if the gel fraction is small, bending strength of the multi-layer sheet may be lowered. Therefore, the gel fraction should preferably be regulated to be 15 ⁇ 70 weight % and more preferably be 18 ⁇ 65 weight %, and the amount of ionizable radiation is usually regulated to be 1 ⁇ 20 Mrad.
  • the ionizable radiation is not particularly limited as far as the ionizable radiation is what has been conventionally used, and ⁇ -rays, ⁇ -rays, ⁇ -rays and electron rays are enumerated, for example.
  • thermoplastic resin is provided with an appropriate crosslinking structure and with fluidity and elongation stress within a required range in the above-mentioned manner, and the obtained multi-layer sheet becomes superior in moldability and surface finishing.
  • inorganic filler may be added to the above-mentioned foam sheet in order to improve bending strength and compression rigidity of the multi-layer sheet.
  • inorganic filler for example, metal oxides like titanium-dioxide and so on; powdered inorganic fillers like calcium carbonate, talc, kaolin clay, mica and so on; inorganic fillers in a state of balloon, Shirasu-balloon, glass balloon, fly ash balloon and so on.
  • talc or mica is preferable.
  • the size of the particles should preferably be 20 ⁇ m or less, and more preferably be 5 ⁇ m or less. If the aspect ratio of the inorganic filler is large, a bending elasticity slope of the obtained thermoplastic resin foam sheet is raised. Therefore, preferable aspect ratio should be 5 or more.
  • the amount is limited to 1 ⁇ 100 weight parts to 100 weight parts of the thermoplastic resin, and should preferably be 5 ⁇ 30 weight parts.
  • oxidation inhibitors such as 2,6-di-t-butyl-p-cresol and so on, or metal deactivators such as methylbenzotriazol and so on may be added to the above-mentioned thermoplastic resin foam sheet.
  • thermoplastic resin foam sheet Most of the bubbles of the above-mentioned thermoplastic resin foam sheet are formed to be spindle-shaped (rugby-ball-shaped), a longitudinal direction of which is directed to a direction of a thickness of the thermoplastic resin foam sheet.
  • the bubbles can be transformed in a state that the bubbles are smoothly and surely swerved in the direction of the thickness of the thermoplastic resin foam sheet by molding stress applied to the thermoplastic resin foam sheet in a direction of the thickness thereof. Accordingly, the thermoplastic resin foam sheet can be accurately formed to be a required form without fail by the molding stress which is applied in the direction of the thickness thereof.
  • the aspect ratio Dz/Dxy of the bubbles of the thermoplastic resin foam sheet is small, the compressive rigidity in the direction of thickness of the obtained thermoplastic resin foam sheet lowers, wherefore the aspect ratio should be limited to 1. 2 or more, should preferably be 1.5 or more, and particularly preferably be 2 or more.
  • the aspect ratio Dz/Dxy of bubbles of the thermoplastic resin foam sheet means a value determined in a manner as described below. Namely, at first, the thermoplastic resin foam sheet is cut in a direction of the thickness. Next, as shown in Fig. 1, a length Dz in the direction of the thickness of the bubble exposed on the cut surface is determined, and a length Dxy, which is a length perpendicular to the direction of the thickness and is along the cut surface, is determined. Then the aspect ratio (Dz/Dxy) of each bubble is calculated. And then a mean value of the obtained aspect ratio (Dz/Dxy) of each of the bubbles is calculated to determine the aspect ratio (Dz/Dxy) of bubbles of the thermoplastic resin foam sheet.
  • object bubbles of the determination in the above-mentioned determination are only what are completely independent without being united with the adjacent bubbles on the cut surface.
  • the adjacent bubbles which are united and integrated into one, and the bubbles whose ends reach the surface of the thermoplastic resin foam sheet are excluded from the object bubbles of the determination.
  • the expansion ratio of the thermoplastic resin foam sheet is high, mechanical strengths of the obtained multi-layer sheet such as compression rigidity, bending strength and so on lower, and if the expansion ratio is low, the lightweight property of the obtained multi-layer sheet lowers. Therefore, the expansion ratio is limited to 5 ⁇ 50cc/g, and should preferably be 10 ⁇ 30cc/g. In the meantime, the expansion ratio of the above-mentioned thermoplastic resin foam sheet is what was determined according to the Japanese Industrial Standard K6767, and is a reciprocal of an apparent density.
  • the compressive strength of the thermoplastic resin foam sheet should preferably be 9.8N/cm 2 or more, more preferably be 14.7N/cm 2 or more, and even more preferably be 29.4N/cm 2 or more.
  • the compressive strength ( ⁇ ) referred to in the present specification means a value indicating resistance against compressive force which is applied in a direction of the thickness, and is found as follows.
  • thermoplastic resin foam sheets of 50mm long and 50mm wide each are layered on one another in order to make a laminate with a thickness of about 25mm.
  • the thickness is then accurately determined to be an initial thickness.
  • the laminate is compressed by 25% of the initial thickness of the laminate (in other words, the laminate is compressed so that the thickness thereof becomes 75% of the initial thickness) at a compressive temperature of 10mm/minute under conditions of a temperature of 20°C and a humidity of 65%RH.
  • the value of load W(N) is determined, and the W is divided by a compressive area A (cm 2 ).
  • Compressive Strength ( ⁇ ) W(N)/A(cm 2 )
  • the multi-layer sheet according to the present invention comprises a reinforcing sheet layered on and integrated with one side of the thermoplastic resin foam sheet, or preferably comprises the reinforcing sheets layered on and integrated with both sides of the thermoplastic resin foam sheet.
  • the reinforcing sheets to be layered on and integrated with the both sides of the thermoplastic resin foam sheet may be of different kind from each other, however, it is preferable to use the same kind of reinforcing sheets which is to be layered on and integrated with the both sides of the thermoplastic resin foam sheet in view of dimensional stability of the obtained multi-layer sheet.
  • the above-mentioned non-meltable fiber means the fiber which do not melt with heat applied in the manufacturing method of the multi-layer sheet or at a time of molding of the multi-layer sheet to provide a required form.
  • the non-meltable fiber means the fiber which maintains form and state thereof irrespective of the heat applied in the manufacturing method of the multi-layer sheet or at the time of molding of the multi-layer sheet to provide the required form.
  • the non-meltable fibers for example, natural fibers such as cotton, kapok, flax, hemp, kenaf, Manila hemp, sisal hemp, New Zealand hemp, maguey, coir and so on; glass fiber; carbon fiber and so on are enumerated.
  • a content of the above-mentioned non-meltable fiber in the reinforcing sheet is high, a content of the thermoplastic resin in the reinforcing sheet becomes comparatively low, wherefore the reinforcing sheet can not be formed to be a state of a sheet in which the non-meltable fibers are interwound with one another well enough. Consequently, the reinforcing sheet can not stably be layered on and integrated with the thermoplastic resin foam sheet. Accordingly, the reinforcing sheet may unexpectedly separate from and leave the thermoplastic resin foam sheet when the multi-layer sheet is transformed. If the content of the non- meltable fiber in the reinforcing sheet is low, tensile strength and bending strength of the reinforcing sheet lower, wherefore 20 ⁇ 90 weight % is preferable, and 25 ⁇ 75 weight % is preferable.
  • the non-meltable fibers in the reinforcing sheet are interwound with one another to the extent more than necessity requires, and when the multi-layer sheet is heated and formed, the interwound non-meltable fibers comprising the reinforcing sheet can not be smoothly swerved along the direction of the surface of the thermoplastic resin foam sheet and the reinforcing sheet is not transformed so as to be a state that follows the thermoplastic resin foam sheet. Consequently, such an unexpected event may happen that the reinforcing sheet separate from and leave the thermoplastic resin foam sheet.
  • the length of the non-meltable fibers should preferably be 30 ⁇ 100mm.
  • thermoplastic resin is not particularly limited as far as the thermoplastic resin is what has been conventionally used as a binder for non-woven fabric.
  • polyolefin-based resins such as polyethylenes like low density polyethylene, straight-chain low density polyethylene, medium density polyethylene, high density polyethylene and so on, polypropylenes like isotactic polypropylene, syndiotactic polypropylene and so on, polybutene, ethylene- ⁇ -olefin copolymer and so on; ethylene-propylene-diene terpolymer; ethylene-vinyl acetate copolymer; ethylene-acrylic ester copolymer; polystyrene-based resins such as polystyrene, polystyrene-based thermoplastic resin elastomer and so on; polyvinyl alcohol-based resins; saturated polyester-based resin
  • ⁇ -olefin propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene and so on are enumerated.
  • a copolymer containing an ethylene component any one of a block copolymer, a random copolymer and a random block copolymer may be acceptable.
  • the melt index should preferably be 20 ⁇ 60g/10minutes.
  • the melt index in the present invention is what was determined according to Japanese Industrial Standard K7210.
  • thermoplastic resin sheet in case the thermoplastic resin sheet is layered on and integrated, as a surface layer, with the above-mentioned reinforcing sheet, part of the thermoplastic resin sheet melts and enter into the reinforcing sheet.
  • the thermoplastic resin sheet in order to keep the reinforcing sheet being covered without fail, the thermoplastic resin sheet, whose melt index is 20g/10minutes or less, is usually used.
  • the melt index of the thermoplastic resin binding the non-meltable fibers of the reinforcing sheet is slightly lowered by the entrance of the thermoplastic resin comprising the surface layer, however, the slight lowering of the melt index has little influence because the amount of the thermoplastic resin binding the non-meltable fibers of the reinforcing sheet from the beginning or the amount of the thermoplastic resin provided by melted thermoplastic resin fibers, which will be described hereinafter, is extremely large compared to the amount of the thermoplastic resin, which comprises the surface layer and enters into the reinforcing sheet.
  • the non-meltable fibers are made to be non-woven fabric by a water-free thermal bond method and a needle punch method, and wet sheet making method, and then melted thermoplastic resin is distributed into a gap among non-meltable fibers which are made to be the non-woven fabric.
  • Another conventional method to manufacture the non-woven fabric is that after interwinding the non-meltable fibers and the thermoplastic resin fibers, the interwound thermoplastic resin fibers are melted to work as a binder, with which the interwound non-meltable fibers are bound together.
  • the per-unit weight should preferably be 10 ⁇ 70g/m 2 , and more preferably be 20 ⁇ 65g/m 2 .
  • Tensile strength of the reinforcing sheet should preferably be 2.94N/cm 2 or more for the following reason.
  • the above-mentioned multi-layer sheet is made by foaming an expandable multi-layer sheet comprising an expandable sheet and the sheet for reinforcement which is layered and integrated with the expandable sheet.
  • foaming of the expandable sheet is limited by the sheet for reinforcement in a direction along the surface of the expandable sheet, while the foaming in a direction of a thickness is free.
  • the direction of the foaming is made directed to the direction of the thickness so as to make the bubbles of the obtained thermoplastic resin foam sheet formed to be spindle-shaped bubbles, whose longitudinal direction is directed to the direction of the thickness of the thermoplastic resin foam sheet.
  • the aspect ratio Dz/Dxy of the spindle-shaped bubbles is regulated to be within the above-mentioned predetermined range.
  • the tensile strength of the reinforcing sheet is small, the tensile strength of the sheet for reinforcement also becomes small. Accordingly, the foaming in the direction along the surface of the expandable sheet can not be effectively regulated by the sheet for reinforcement, the aspect ratio Dz/Dxy of the bubbles of the obtained foam sheet can not be within the predetermined range, and the obtained multi-layer sheet may not be provided with required compressive rigidity.
  • the coefficient of linear expansion of the obtained multi-layer sheet should preferably be 5 ⁇ 10 -5 /°C or less, and more preferably be 1 ⁇ 10 -5 /°C or less.
  • the surface layer may be layered on and integrated with a surface of the above-mentioned reinforcing sheet, and by additionally layering and integrating the surface layer on the surface of the reinforcing sheet like this, the surface layer works as a binder to more firmly bind the non-meltable fibers of the reinforcing sheet with one another, enabling the coefficient of linear expansion to lower, and as a result the obtained multi-layer sheet can be the one which is provided with high dimensional stability.
  • the reinforcing sheet comprising the non-woven fabric is formed to be a state in which non-meltable fibers are disorderly interwound with one another, the surface of the reinforcing sheet is formed unevenly in which the non-meltable fibers disorderly project from the surface. Therefore, when a surface material is layered on the surface of the reinforcing sheet, it may happen that the surface material may not be stably layered due to the uneven surface attributed to the non-meltable fibers.
  • the uneven surface of the above-mentioned reinforcing sheet attributed to the non-meltable fibers of the reinforcing sheet is covered and concealed to provide a smooth surface.
  • the smooth surface enables the surface material to be stably and firmly layered on the surface of the multi-layer sheet, which makes integration of the surface material and the multi-layer sheet so firm as to prevent, without fail, such an unexpected event as separation and leaving of the surface material from the multi-layer sheet during molding method of the multi-layer sheet. Accordingly, even when the multi-layer sheet with the surface material layered on one side thereof is molded, it is possible to mold the multi-layer sheet by applying strong molding pressure to provide a complex shape accurately and without fail.
  • the surface layer may be layered on and integrated with one of the reinforcing sheets.
  • the above-mentioned surface layer is not particularly limited as far as the surface layer is what can cover the reinforcing sheet.
  • the surface layer should preferably comprises such thermoplastic resins as polystyrene, polyethylene, polypropylene, polybutene, nylon, polyethylene terephthalate and so on, and should preferably be compatible with one or both of the thermoplastic resin of the reinforcing sheet and the thermoplastic resin comprising the thermoplasic resin foam sheet.
  • thermoplastic resin comprising the above-mentioned surface layer and the thermoplastic resin comprising the above-mentioned thermoplastic resin foam sheet are made to be compatible, and by having the thermoplastic resin comprising the above-mentioned surface layer entered into the gap of the non-meltable fibers comprising the above-mentioned reinforcing sheet to reach the surface of the above-mentioned thermoplastic resin foam sheet in order to be integrated with the thermoplastic resin foam sheet, the above-mentioned reinforcing sheet can firmly be kept layered on the surface of the thermoplastic resin foam sheet stably.
  • the multi-layer sheet can be molded to provide a complex shape without fail by applying stronger molding pressure onto the multi-layer sheet without causing such an unexpected event like letting the reinforcing sheet separate from and leave the thermoplastic resin foam sheet.
  • the thermoplastic resin comprising the surface layer, the thermoplastic resin of the reinforcing sheet (the thermoplastic resin fibers of the sheet for reinforcement) and the thermoplastic resin comprising the thermoplastic resin foam sheet are made to be compatible with one another, the above-mentioned actions and effects can be demonstrated more certainly.
  • the above-mentioned surface layer covers the non-meltable fibers comprising the reinforcing sheet in a state of wrapping-up, when the multi-layer sheet is heated and molded, the non-meltable fibers comprising the reinforcing sheet are put in a free state as if the non-meltable fibers float in the thermoplastic resin.
  • the interwound non-meltable fibers can be swerved smoothly in the direction along the surface of the thermoplastic resin foam sheet, following up the transformation of the thermoplastic resin foam sheet of the multi-layer sheet, whereby the reinforcing sheet is transformed in a direction along the surface of the thermoplastic resin foam sheet smoothly and without fail according to the transformation of the thermoplastic resin foam sheet, and such an unexpected event does not happen that the reinforcing sheet separates from and leaves the surface of the thermoplastic resin foam sheet. Therefore, there is an excellent effect that when the multi-layer sheet is formed the multi-layer sheet can be molded to provide a complex shape without fail by applying stronger molding pressure onto the multi-layer sheet.
  • the thickness of the surface layer should preferably be 10 ⁇ 200 ⁇ m.
  • a manufacturing method of the multi-layer sheet is explained hereinafter.
  • the manufacturing method of the multi-layer sheet is not particularly limited.
  • the following methods are suggested. Namely, 1 ⁇ a modified thermoplastic resin is made by adding a multifunctional monomer to a thermoplastic resin to have the thermoplastic resin reacted with the multifunctional monomer, a pyrolysis-type foaming agent is added to the modified thermoplastic resin, the modified thermoplastic resin is melted and kneaded at a temperature lower than a decomposition temperature of the pyrolysis-type foaming agent, and after an expandable sheet is formed, an expandable multi-layer sheet is formed by having a sheet for reinforcement comprising non-woven fabric in which non-meltable fibers and synthetic resin fibers are interwound with one another layered on one side of the expandable sheet, the expandable multi-layer sheet is heated at a temperature higher than a reaction temperature of the multifunctional monomer and higher than a decomposition temperature of the pyrolysis-type foaming agent to have this foam
  • An expandable resin composite containing a thermoplastic resin, a crosslinking agent and a pyrolysis-type foaming agent is melted and kneaded at a temperature lower than a reaction temperature of the crosslinking agent and the decomposition temperature of the pyrolysis-type foaming agent and an expandable sheet is formed, and before or after the expandable sheet is provided with a crosslinking structure by applying electrolytically dissociatable radiation to the expandable sheet, an expandable multi-layer sheet is formed by having a sheet for reinforcement, comprising a non-woven fabric, in which non-meltable fibers and synthetic resin fibers are interwound with one another, layered on one side of the expandable sheet, the expandable multi-layer sheet is heated to a temperature higher than the decomposition temperature of the pyrolysis-type foaming agent, and the synthetic resin fibers of the reinforcing sheet are melted to bind the non-meltable fibers with one another and thus the multi-layer sheet is provided.
  • a modified thermoplastic resin is made by adding a multifunctional monomer to a thermoplastic resin and then having the thermoplastic resin reacted with the multifunctional monomer, a pyrolysis-type foaming agent is added to the modified thermoplastic resin which is melted and kneaded at the temperature lower than the decomposition temperature of the pyrolysis-type foaming agent to form an expandable sheet, and after an expandable multi-layer sheet is formed by having a sheet for reinforcement, comprising a non-woven fabric in which non-meltable fibers are interwound with one another and the non-meltable fibers are bound together by the thermoplastic resin, layered on one side of the expandable sheet, the expandable multi-layer sheet is heated to the temperature higher than the reaction temperature of the multifunctional monomer and the decomposition temperature of the pyrolysis-type foaming agent and in order to provide the multi-layer sheet.
  • An expandable resin composite containing a thermoplastic resin, a crosslinking agent and a pyrolysis-type foaming agent is melted and kneaded at the temperature lower than the reaction temperature of the crosslinking agent and the decomposition temperature of the pyrolysis-type foaming agent to form the expandable sheet, and before or after the expandable sheet is provided with the crosslinking structure by applying electrolytically dissociatable radiation to the expandable sheet, an expandable multi-layer sheet is formed by having a sheet for reinforcement, comprising a non-woven fabric in which non-meltable fibers are interwound with one another and non-meltable fibers are bound together by the thermoplastic resin, layered on one side of the expandable sheet, and then the expandable multi-layer sheet is heated to the temperature higher than the decomposition temperature of the pyrolysis-type foaming agent and thus the multi-layer sheet is provided.
  • the above-mentioned manufacturing methods 1 ⁇ and 2 ⁇ are preferable in view of excellent mold
  • the sheet for reinforcement and the expandable sheet may be integrated in advance, or the sheet for reinforcement may be layered on the expandable sheet without integrating the expandable sheet with the sheet for reinforcement, and when the expandable multi-layer sheet is foamed, the thermoplastic resin foam sheet obtained from the expandable sheet and the sheet for reinforcement may be integrated with each other by utilizing the foaming pressure.
  • the above-mentioned pyrolysis-type foaming agent is not particularly limited as far as the pyrolysis-type foaming agent is what is generally used for manufacturing foamed products.
  • such inorganic pyrolysis-type foaming agents as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, azide compounds and so on
  • organic pyrolysis-type foaming agents as azodicarbonamide, azobisisobutylonitryl, dinytrosopenta methylene tetramine, benzenesulphonyl hydrazide, toluensulfonyl hydrazide, 4,4-oxybis (benzenesulphonyl hydrazide), azodicarboxylic acid barium, trihydrazinotriazine, p-toluene-sulfonyl semicarbazide and so on, are enumerated.
  • the amount of the foaming agent should preferably be 1 ⁇ 50 weight parts to 100 weight parts of the thermoplastic resin.
  • Specific manufacturing methods of the expandable sheet are, for example, as follows. 1 ⁇ After peroxide is added to the thermoplastic resin and the multifunctional monomer as necessity requires, the thermoplastic resin and the multifunctional monomer are fed to the extruder to allow the multifunctional monomer to react to the thermoplastic resin to provide the modified thermoplastic resin, and after the pyrolysis-type foaming agent is added to the modified thermoplastic resin in the extruder, the modified thermoplastic resin is melted and kneaded at a temperature lower than the decomposition temperature of the pyrolysis-type foaming agent, and is extruded to make a form of sheet in order to manufacture the expandable sheet.
  • thermoplastic resin, the crosslinking agent and the pyrolysis-type foaming agent are fed to the extruder, melted and kneaded at a temperature lower than the reaction temperature of the crosslinking agent and the decomposition temperature of the pyrolysis-type foaming agent, and extruded to make a form of sheet in order to manufacture the expandable sheet.
  • the electrolytically dissociatable radiation is applied to provide the thermoplastic resin, which comprises the expandable sheet, with the crosslinking structure as above-mentioned, before or after the sheet for reinforcement is layered on one side of the expandable sheet in a manner as will be described hereinafter.
  • the sheet for reinforcement is layered on one side or on both sides of the expandable sheet.
  • the sheet for reinforcement is the non-woven fabric in which non-meltable fibers and the thermoplastic resin fibers are interwound with one another, or is the non-woven fabric in which the non-meltable fibers are interwound with one another and the non-meltable fibers are bound together with the thermoplastic resin.
  • a conventional manufacturing method of the non-woven fabric is adopted. For example, a water-free thermal bond method and a needle punch method, and a wet sheet making method, in which the non-meltable fibers and the thermoplastic resin fibers are treated, are enumerated.
  • a conventional manufacturing method of the non-woven fabric is adopted.
  • non-meltable fibers are made to be the non-woven fabric by a water-free thermal bond method and a needle punch method, and a wet sheet making method, and then the melted thermoplastic resin is distributed into a gap among non-meltable fibers which was made to be the non-woven fabric, by which the non-meltable fibers are bound together with the thermoplastic resin.
  • thermoplastic resin fibers for example, polyolefin-based resins such as polyethylenes like low density polyethylene, straight-chain low density polyethylene, medium density polyethylene, high density polyethylene and so on, polypropylenes like isotactic polypropylene, syndiotactic polypropylene and so on, polybutene, ethylene- ⁇ -olefin copolymer and so on; ethylene-propylene-diene terpolymer; ethylene-vinyl acetate copolymer; ethylene-acrilic ester copolymer; such polystyrene-based resins as polystyrene, polystyrene-based thermoplastic resin elastomer and so on; polyvinyl-alcohol-based resins; saturated polyester-based resins; unsaturated polyester-based resins; such acrylic resins as polymethyl(metha)acrylate, polybutyl(metha)acrylate, poly-n-tetradec
  • the reinforcing sheet is formed by melting the thermoplastic resin fibers of the sheet for reinforcement by heating of the expandable multi-layer sheet in later process, and then by binding the interwound non-meltable fibers together by using the melted thermoplastic resin as the binder.
  • the reinforcing sheet is layered on and integrated with the thermoplastic resin foam sheet provided by foaming the expandable sheet.
  • the sheet for reinforcement in which the non-meltable fibers are interwound with one another and the non-meltable fibers are bound together by the thermoplastic resin is used, the sheet for reinforcement is made to be the reinforcing sheet, and the reinforcing sheet is layered on and integrated with the thermoplastic resin foam sheet provided by foaming the expandable sheet.
  • thermoplastic resin fibers of the sheet for reinforcement are melted, whereby a form and a state of the fibers almost disappear, and work as a binder to bind the non-meltable fibers together.
  • the thermoplastic resin fibers can be positioned in advance in the gap formed by the non-meltable fibers interwound with one another.
  • thermoplastic resin to work as the binder By melting the thermoplastic resin fibers positioned in the gap of the interwound non-meltable fibers, the thermoplastic resin to work as the binder can be supplied to the minute gap of the interwound non-meltable fibers, and the non-meltable fibers can be bound together evenly, finely and firmly, whereby the obtained reinforcing sheet can be the one in which non-meltable fibers are bound together evenly and firmly by the thermoplastic resin.
  • the reinforcing sheet which can be obtained in the above-mentioned manner by using the sheet for reinforcement comprising the non-woven fabric, in which the non-meltable fibers and the thermoplastic resin fibers are interwound with one another, has excellent bending strength.
  • thermoplastic resin as a binder being distributed evenly all over the reinforcing sheet, intervenes, even when the multi-layer sheet is heated and molded, the melted thermoplastic resin which intervenes in the gap of the non-meltable fibers works as a lubricant, whereby the non-meltable fibers are swerved smoothly and firmly along the direction of the surface of the thermoplastic resin foam sheet following the transformation of the thermoplastic resin foam sheet of the multi-layer sheet.
  • the above-mentioned reinforcing sheet is smoothly transformed following the transformation of the thermoplastic resin foam sheet, and such an unexpected event does not happen that the reinforcing sheet separates from and leaves the surface of the thermoplastic resin foam sheet, wherefore the multi-layer sheet can be molded to provide a complex shape without fail and accurately by applying strong molding stress onto the multi-layer sheet.
  • the per-unit weight should preferably be 10 ⁇ 70g/m 2 , and more preferably be 20 ⁇ 50g/m 2 .
  • the per-unit weight of the sheet for reinforcement should preferably be regulated to be 8 ⁇ 65g/m 2 , taking into consideration an amount of the increase resulting from the part of the thermoplastic resin sheet entering into the sheet for reinforcement.
  • the reinforcing sheet may unexpectedly separate from and leave the thermoplastic resin foam sheet when the multi-layer sheet is transformed. If the content of the non- meltable fiber in the sheet for reinforcement is low, tensile strength and bending strength of the reinforcing sheet lower, wherefore 20 ⁇ 90 weight % is preferable, and 25 ⁇ 75 weight % is preferable.
  • the thermoplastic resin sheet is layered on the surface of the sheet for reinforcement in a manner as will be mentioned hereinafter, part of the thermoplastic resin sheet enters into the sheet for reinforcement and the content of the non-meltable fibers in the obtained reinforcing sheet comparatively lowers. Therefore, taking into consideration the amount of the increase resulting from the part of the thermoplastic resin sheet entering into the sheet for reinforcement, the content of the non-meltable fibers should preferably be 22 ⁇ 95 weight % and preferably be 27 ⁇ 80 weight %.
  • Processes to layer and integrate the sheet for reinforcement on and with one side or on both sides of the expandable sheet are, for example, as follows. 1 ⁇ The sheet for reinforcement is pressed onto the surface of the expandable sheet while being heated for layering and integration. 2 ⁇ The sheet for reinforcement is pressed onto the surface of the expandable sheet, which is in a state of melt, for layering and integration. In other words, the expandable sheet is extruded from a T-die mounted to a tip of the extruder.
  • the sheet for reinforcement is placed on one side of the expandable sheet, whose surface is in a state of melt soon after being extruded, and is supplied between a pair of cooling rolls by which the expandable sheet and the sheet for reinforcement are held and are integrated with each other, whereby the sheet for reinforcement is layered on and integrated with one side of the expandable sheet.
  • the expandable sheet and the sheet for reinforcement are layered and integrated together via an adhesive.
  • the above-mentioned 1 ⁇ is preferable because fine regulation of a thickness of the expandable multi-layer sheet can be done.
  • an additional surface layer is layered on and integrated with the surface of the reinforcing sheet
  • a surface sheet and the sheet for reinforcement is layered on one side of the expandable sheet in a manner that the sheet for reinforcement is positioned inside, and then heated to a softening temperature of the surface sheet or over in order to have the sheet for reinforcement and the surface sheet layered on and integrated with the expandable sheet. And the surface sheet is melted to be layered on and integrated with the reinforcing sheet obtained from the sheet for reinforcement to structure the layer surface.
  • thermoplastic resin sheet comprising such thermoplastic resins and the non-woven fabric formed with the fibers comprising such thermoplastic resins as polyolefin-based resins such as polyethylenes like low density polyethylene, straight-chain low density polyethylene, medium density polyethylene, high density polyethylene and so on, polypropylenes like isotactic polypropylene, syndiotactic polypropylene and so on, polybutene, ethylene- ⁇ -olefin copolymer and so on; as ethylene-propylene-diene terpolymer; as ethylene-vinyl acetate copolymer; as ethylene-acrylic ester copolymer; as polystyrene-based resins like polystyrene, polystyrene-based thermoplastic resin elastomer and so on; as polyvinyl alcohol-based resins; as saturated polyester-based resins; as unsaturated polyester-based resins; as acrylic-based resins
  • the polyolefin-based resin sheet and the non-woven fabric made of the polyolefin-based resin fibers are preferable.
  • the non-woven fabric comprising the fibers made of the thermoplastic resins is used as the surface sheet, the fibers comprising the surface sheet are melted by heat wherefore the form and state of the fibers disappear, and the obtained surface layer is formed to be a smooth surface.
  • the surface sheet also includes what is called a film which is thin.
  • an ordinary heating apparatus which has been conventionally used for manufacturing foamed products is used.
  • a roll-type heating apparatus or a belt-type heating apparatus in which the expandable multi-layer sheet is supplied between a pair of heater-rolls or a pair of heater-belts arranged oppositely to each other to heat the expandable multi-layer sheet, a hot air thermostat in which hot blast is applied to the expandable multi-layer sheet, an oil bath, a metal bath and salt bath in which the expandable multi-layer sheet is bathed in heat are enumerated.
  • the expandable sheet of the expandable multi-layer sheet is foamed in a manner as mentioned above, as the sheet for reinforcement is layered on and integrated with one side of the expandable sheet, in foaming of the expandable sheet, foaming in a direction along the surface is limited by the sheet for reinforcement, and on the other hand foaming in a direction of the thickness is in a state of free-foaming without being limited by the sheet for reinforcement.
  • the foaming direction of the above-mentioned expandable sheet is limited to be directed in the direction of the thickness, and the bubbles of the thermoplastic resin foam sheet provided by foaming the expandable sheet are formed to be spindle-shaped, in which the longitudinal direction is directed to the direction of the thickness of the expandable sheet and the bubbles have an aspect ratio Dz/Dxy within a predetermined range.
  • thermoplastic resin foam sheet most of the bubbles of the thermoplastic resin foam sheet are formed to be spindle-shaped whose longitudinal direction is directed to the direction of the thickness of the thermoplastic resin foam sheet, wherefore, the obtained multi-layer sheet has an excellent compressive strength in the direction of the thickness, while maintaining a lightweight property as the multi-layer sheet partly comprises the thermoplastic resin foam sheet.
  • the multi-layer sheet is also excellent in bending strength as the multi-layer sheet comprises the foam sheet and the reinforcing sheet, which reinforcing sheet comprises the non-woven fabric formed with the interwound non-meltable fibers bound with the thermoplastic resin fibers, and which reinforcing sheet is layered on and integrated with one side of the foam sheet of the multi-layer sheet.
  • the multi-layer sheet comprises the thermoplastic resin foam sheet, which is excellent in mouldability, on and with one side of which the reinforcing sheet is layered and integrated
  • the multi-layer sheet can be molded to be a required shape by such general molding methods as a thermopressing method, a cold-press method, vacuum press method and so forth.
  • the thermopressing method means a method in which thermoforming is carried out with an ordinary compression molding press.
  • the cold press method means a method in which the surface of the multi-layer sheet is heated to exceed a softening point of the foam sheet, namely, to be specific, to a surface temperature of 160 ⁇ 210°C and then the multi-layer sheet is formed in the male-female metal mold which is kept at a temperature less than the softening point of the foam sheet, namely and specifically at 10 ⁇ 70°C.
  • the heating temperature of the multi-layer sheet in the above-mentioned cold press method is high, the thermoplastic resin foam sheet of the multi-layer sheet is melted, the aspect ratio of the thermoplastic resin foam sheet lowers, and the compressive strength of the obtained molding product may lower. If the temperature is low, molding of the multi-layer sheet becomes insufficient and may not be molded to a required shape, or mold distortion remains in the obtained molding product and the dimensional stability of the molding product may lower. Therefore, 160 ⁇ 210°C is preferable.
  • the heating temperature of the male-female metal mold in the above-mentioned cold press method is high, cooling of the obtained molding product becomes insufficient and dimension of the molding product may change as time goes by. If the temperature is low, molding of the multi-layer sheet becomes insufficient and may not be molded to a required shape, or mold distortion remains in the obtained molding product and the dimensional stability of the molding product may lower. Therefore, 10 ⁇ 70°C is preferable.
  • the bending elasticity slope of the above-mentioned multi-layer sheet is small, there is a misgiving that a worker may bend and break the multi-layer sheet by mistake when the worker handles the multi-layer sheet. Therefore, the bending elasticity slope is limited to 78.4N/50mm/cm or above, should preferably be 117.6n/50mm/cm and more preferably be 156.8N/50mm/cm.
  • the bending elasticity slope of the multi-layer sheet represents a value indicating a resistance against a load applied to the multi-layer sheet in the direction of the thickness thereof, and was determined on a piece of the multi-layer sheet of 15cm long, 50cm wide and 6.5cm thick, according to Japanese Industrial Standard K7203.
  • the per-unit strength should preferably be 98N/50mm/cm/kg/m 2 or more, and more preferably be 117.6 N/50mm/cm/kg/m 2 or more.
  • the per-unit strength is found by dividing the bending elasticity slope by the per-unit weight.
  • the coefficient of linear expansion of the multi-layer sheet should preferably be 6.0 ⁇ 10 -5 /°C or less.
  • thermoplastic resin in the reinforcing sheet is the thermoplastic resin binding the non-meltable fibers of the sheet for reinforcement together, the melted thermoplastic resin fibers of the sheet for reinforcement, or the thermoplastic resin comprising the surface layer, which was entered into the reinforcing sheet.
  • thermoplastic resin in the reinforcing sheet is the thermoplastic resin binding the non-meltable fibers of the sheet for reinforcement together, the melted thermoplastic resin fibers of the sheet for reinforcement, or the thermoplastic resin comprising the surface layer, which was entered into the reinforcing sheet.
  • such a point as above is not particularly a matter of question in the present invention. Namely, it is sufficient as far as the interwound non-meltable fibers comprising the reinforcing sheet of the obtained multi-layer sheet are bound together with the thermoplastic resin in one way or another.
  • the multi-layer sheet according to the present invention comprises the thermoplastic resin foam sheet and the reinforcing sheet layered on and integrated with at least one side of the thermoplastic resin foam sheet, in which the reinforcing sheet comprises the non-woven fabric where non-meltable fibers are interwound with one another and are bound together with synthetic resin, and in which bubbles of the thermoplastic resin foam sheet have an aspect ratio Dz/Dxy of 1.2 or more, and an expansion ratio of 5 ⁇ 50cc/g, the multi-layer sheet has excellent bending strength and compressive strength in a direction of the thickness thereof.
  • thermoplastic resin foam sheet of the multi-layer sheet as the longitudinal direction of the bubbles is made directed to the direction of the thickness of the multi-layer sheet and the bubbles have the aspect ratio Dz/Dxy within a predetermined range, the thermoplastic resin foam sheet maintains the excellent compressive strength in the direction of the thickness even when the expansion ratio is raised.
  • thermoplastic resin foam sheet the one with high expansion ratio may be used, which is excellent in bending strength and compressive strength while maintaining the high lightweight property.
  • the multi-layer sheet according to the present invention has an excellent dimensional stability.
  • the per-unit weight of the reinforcing sheet is made to be 10 ⁇ 70g/m 2
  • the multi-layer sheet is heated and molded, such an unexpected event does not happen that the thermoplastic resin foam sheet in a softened state sags down with a weight of the reinforcing sheet and the aspect ratio of the bubbles thereof lowers, whereby the molding product with the excellent compressive strength can be obtained.
  • the reinforcing sheet in which non-meltable fibers are interwound in a good condition and which has excellent tensile strength, can be layered on and integrated with the one side of the thermoplastic resin foam sheet stably and firmly, wherefore such an event does not happen that the reinforcing sheet unexpectedly separates from and leaves the surface of the thermoplastic resin foam sheet. Accordingly, the multi-layer sheet can be molded to provide a complex shape by applying strong molding stress.
  • the non-meltable fibers in the reinforcing sheet are interwound with one another to such an extent that the non-meltable fibers can be swerved smoothly in the direction along the surface of the thermoplastic resin foam sheet and are interwound firmly, wherefore the obtained multi-layer sheet has an excellent bending strength.
  • the reinforcing sheet can be smoothly swerved in the direction along the surface of the thermoplastic resin foam sheet following the transformation of the thermoplastic resin foam sheet, the reinforcing sheet smoothly follows up the transformation of the thermoplastic resin foam sheet and is transformed, wherefore such an unexpected event does not happen that the reinforcing sheet separates from and leaves the surface of the thermoplastic resin foam sheet. Accordingly, the multi-layer sheet can be molded to provide a complex shape by applying strong molding stress.
  • thermoplastic resin binding the non-meltable fibers of the reinforcing sheet together works as a lubricant and helps the non-meltable fibers being swerved in a direction along the surface of the thermoplastic resin foam sheet. Accordingly, the non-meltable fibers smoothly and without fail follows up the transformation of the above-mentioned thermoplastic resin foam sheet and are swerved in a direction along the surface of the thermoplastic resin foam sheet.
  • the reinforcing sheet smoothly follows up the transformation of the thermoplastic resin foam sheet and transforms wherefore the reinforcing sheet does not separate from and leaves the thermoplastic resin foam sheet unexpectedly. Accordingly, the multi-layer sheet can be molded to provide a complex shape by applying a strong molding stress.
  • the surface layer is layered on the surface of the reinforcing sheet, as the unevenness attributed to the non-meltable fibers comprising the reinforcing sheet can be covered and concealed by the surface layer to provide a smooth surface. Accordingly, in case a surface material or the like is layered on the multi-layer sheet, the surface material or the like can be layered on and integrated with the smooth surface layer firmly and stably in a state of close adherence.
  • the multi-layer sheet can be molded to provide a complex shape accurately and without fail by applying strong molding stress on the multi-layer sheet.
  • the non-meltable fibers comprising the reinforcing sheet are in a state of being covered with the thermoplastic resin existing in the reinforcing sheet as the binder and with the thermoplastic resin comprising the surface layer.
  • the non-meltable fibers comprising the reinforcing sheet are in such a state as floating in these melted thermoplastic resins. Accordingly, the non-meltable fibers comprising the above-mentioned reinforcing sheet can be swerved very smoothly in a direction along the surface of the thermoplastic resin foam sheet following up the transformation of the thermoplastic resin foam sheet.
  • the above-mentioned reinforcing sheet smoothly and without fail follows up the transformation of the thermoplastic resin foam sheet of the multi-layer sheet, and the reinforcing sheet does not unexpectedly separate from and leave the surface of the thermoplastic resin foam sheet, wherefore the multi-layer sheet can be molded to provide a complex shape accurately and without fail by applying a strong molding stress on the multi-layer sheet.
  • the reinforcing sheet has an excellent tensile strength, wherefore the obtained multi-layer sheet also has such mechanical strengths like an excellent bending strength, an excellent compressive strength and so on.
  • thermoplastic resin comprising the surface layer enters into the reinforcing sheet and is integrated with the thermoplastic resin foam sheet
  • the reinforcing sheet is covered with the surface layer and is integrated with the surface of the thermoplastic resin foam sheet firmly and without fail.
  • the reinforcing sheet does not separate from and leave the surface of the thermoplastic resin foam sheet unexpectedly, wherefore the multi-layer sheet can be molded to provide a complex shape accurately and without fail by applying a strong molding stress on the multi-layer sheet.
  • the sheet for reinforcement comprising the non-woven fabric formed in a manner that the non-meltable fibers and the thermoplastic resin fibers are interwound with one another, is layered on one side of the expandable sheet and thereafter the expandable sheet is foamed and the synthetic resin fibers of the sheet for reinforcement is melted to work as a binder binding the non-meltable fibers together, the thermoplastic resin fibers are arranged in the minute gap among the interwound non-meltable fibers in advance, and the thermoplastic resin fibers in this state are melted to be able to be distributed in the gap among the interwound non-meltable fibers to work as the binder, whereby the non-meltable fibers of the obtained reinforcing sheet are bound together evenly, finely and firmly by the thermoplastic resin, and has an excellent bending strength, and the obtained multi-layer sheet is also excellent in such mechanical strengths as bending strength, compressive strength and so on.
  • thermoplastic resin working as a binder in the reinforcing sheet is evenly distributed in the reinforcing sheet, and the non-meltable fibers are evenly bound together overall by the evenly distributed thermoplastic resin. Therefore even when the reinforcing sheet is transformed according to the transformation of the thermoplastic resin form sheet, the non-meltable fibers are evenly swerved overall in a direction of the surface of the thermoplastic resin foam sheet and such an unexpected event does not happen that distortion remains in part of the reinforcing sheet. Consequently, the molding product provided by molding the multi-layer sheet has an excellent dimensional stability.
  • the non-meltable fibers in the reinforcing sheet are swerved smoothly according to the transformation of the thermoplastic resin foam sheet, and the reinforcing sheet is smoothly transformed according to the transformation of the thermoplastic resin foam sheet and does not separate from and leave the surface of the thermoplastic resin foam sheet unexpectedly, wherefore the multi-layer sheet can be molded to provide a complex shape accurately and without fail by applying a strong molding stress on the multi-layer sheet.
  • the excellent multi-layer sheet which has excellent mechanical strengths such as the above-mentioned bending strength, compressive strength and so on, lightweight property, dimensional stability and moldability, can be manufactured easily and without fail.
  • Fig. 1 shows a cross-sectional shape of the bubbles of the thermoplastic resin foam sheet of the multi-layer sheet cut in a direction of a thickness
  • Fig. 2 shows a longitudinal sectional view of the multi-layer sheet
  • Fig. 3 is a model side view showing a belt-type heating apparatus used when the multi-layer sheet is manufactured
  • Fig. 4 is a perspective view showing a male-female metal mold which is used when the multi-layer sheet is molded.
  • Fig. 5 is a perspective view showing the molding product provided by using the male-female metal mold shown in Fig. 4.
  • a manufacturing apparatus was used in which a same-directional rotating twin screw extruder (manufactured by Nippon Steel Co., Ltd., trade name “TEX-44", referred to as “second extruder” hereinafter) which is connected to a tip of a same-directionally rotating twin screw extruder (Plastic Engineering Research Institute, trade name "BT40”, referred to as "first extruder”) via an adaptor.
  • a same-directional rotating twin screw extruder manufactured by Nippon Steel Co., Ltd., trade name "TEX-44”, referred to as "second extruder” hereinafter
  • the first extruder is equipped with a self-wiping double screw whose L/D is 35 and whose D (diameter) is 39mm.
  • a cylinder barrel is sectioned into four barrels from a first barrel at upper reaches to a fourth barrel at lower reaches of the extruder, and an adaptor is equipped at a tip of the fourth barrel which adaptor can be continuously connected to the TEX-44 type same-directionally rotating twin screw extruder.
  • the fourth barrel is equipped with a vacuum vent.
  • a temperature of the first barrel of the first extruder was set to be 180°C
  • a temperature of the second to the fourth barrels was set to be 220°C
  • number of rotation of the screw was set to be 150rpm.
  • the above-mentioned second extruder is equipped with a self-wiping double screw, whose L/D was 45.5 and whose D was 47mm.
  • the cylinder barrel is sectioned into twelve barrels from a first barrel at upper reaches to a twelfth barrel at lower reaches of the extruder, and at a tip of the twelfth barrel a coat-hanger die of 1500mm wide is equipped.
  • the sixth barrel is equipped with a side-feeder in order to feed a foaming agent
  • the eleventh barrel is equipped with a vacuum vent in order to collect components volatilized in the cylinder barrel.
  • the first barrel of the second extruder was cooled all the time and a temperature of the second barrel to the fourth barrel was set to be 150°C, a temperature of the fifth barrel to the eighth barrel was set to be 170°C, a temperature of the ninth barrel to the twelfth barrel was set to be 180°C, a temperature of the adaptor and the coat- hanger die was set to be 160°C and a number of rotation of the screw was set to be 40rpm.
  • the amount of feed of the above-mentioned polypropylene was 10kg/h
  • the amount of feed of the p-quinone dioxime was 0.08kg/h.
  • the pellets of the modified polypropylene fed from the hopper of the first barrel of the second extruder were made in a manner as follows. Namely, instead of using the adaptor which was used in the above-mentioned method to connect the second extruder to the tip of the first extruder, the one which was provided with a three-hole strand die was used.
  • p-quinone dioxime manufactured by Ouchishinko Chemical Co.
  • VALNOC GM-P trade name "VALNOC GM-P" as a multifunctional monomer were fed to the hopper provided to be integrated at the rear end of the first barrel of the extruder and were melted and kneaded. Then after the modified polypropylene was extruded from the three-hole strand die, the extruded modified polypropylene was cooled with water, and was cut with a pelletizer into a predetermined length to obtaine the modified polypropylene in a state of pellet. An amount of supply of the above-mentioned polypropylene was 10kg/h, and an amount of the p-quinone dioxime was 0.08kg/h.
  • the above-mentioned laminated surface material was layered on both surfaces of the above-mentioned expandable polypropylene sheet in a manner that the sheet for reinforcement comes inside in order to provide an expandable multi-layer sheet. Then the expandable multi-layer sheet was fed to a belt-type heating apparatus and was heated to 230°C in order to foam the expandable polypropylene sheet.
  • thermoplastic resin foam sheet provided by foaming the expandable polypropylene sheet
  • the former and the latter were integrated with each other, and were cooled to provide a multi-layer sheet of 6.5mm thick comprising a reinforcing sheet and a surface layer which were so layered on and integrated with both surfaces of a polypropylene foam sheet that each of the reinforcing sheet came inside.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with both surfaces of the polypropylene foam sheet (A1). And the carbon fibers comprising the above-mentioned reinforcing sheet (A2) were firmly bound together having polypropylene, being melted polypropylene fibers, as a binder. The carbon fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3), and each surface of the multi-layer sheet (A) was formed to be a smooth surface.
  • the homo-type polypropylene comprising the surface layer (A3) of the multi-layer sheet (A) entered into the reinforcing sheet (A2) to reach the surface of the polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the above-mentioned belt-type heating apparatus comprises a preheating zone 1, a foaming zone 2, a cooling zone 3, and a pair of conveyer belts 4, 4 which are arranged extendedly over these three zones leaving a predetermined clearance in an up-and-down direction.
  • the expandable multi-layer sheet was placed on the upper surface of the lower conveyer belt of the pair of the conveyer belts 4,4 and the expandable multi-layer sheet was sent into the preheating zone 1, the foaming zone 2 and the cooling zone 3 in this order.
  • the above-mentioned expandable multi-layer sheet was foamed between inner surfaces of the conveyer belts 4, 4 facing to each other, and while foaming of the above-mentioned expandable multi-layer sheet 5 was in progress, the expandable multi-layer sheet 5 was held and pressed from up-and-down directions between the inner surfaces of the conveyer belts 4, 4 facing to each other in order to press the sheet for reinforcement against each of both sides of the expandable polypropylene sheet to be integrated therewith.
  • the multi-layer sheet was obtained in which the reinforcing sheet and the surface layer were layered on each of both sides of the polypropylene foam sheet in this order.
  • a temperature of the preheating zone was set to be 190°C
  • a temperature of the foaming zone was set to be 230°C
  • a temperature of the cooling zone was set to be 25°C
  • a linear velocity of supply of the expandable polypropylene sheet into the belt-type heating apparatus was set to be 0.5m/minute.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the glass fibers comprising the above-mentioned reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the glass fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • the homo-type polypropylene comprising the surface layer (A3) of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2) and reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the kenaf fibers comprising the reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the kenaf fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer (A3) of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2) and reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the multi-layer sheet was obtained in a similar manner as in the embodiment 1 except that as the surface film, non-woven fabric of per-unit weight of 25g/m 2 was used which comprises core-sheath type fibers interwound with one another.
  • the core-sheath type fiber comprises polyester as a core and polyethylene as a sheath.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the carbon fibers comprising the reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the carbon fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces. In the meantime, the above-mentioned core-sheath type fibers were melted and shape and state of the fibers completely disappeared to form the smooth surface layer (A3).
  • the homo-type polypropylene comprising the surface layer (A3) of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2) and reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the glass fibers comprising the reinforcing sheet (A2) were firmly bound together with the acrylate-based emulsion resin as a binder. In addition, the glass fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer (A3) of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2) and reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet of the obtained multi-layer sheet was firmly layered on and integrated with each of both sides of the polypropylene foam sheet.
  • the carbon fibers comprising the reinforcing sheet were firmly bound together with the acrylate-based emulsion resin as a binder.
  • the carbon fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet were formed to be smooth surfaces.
  • the homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet entered into the reinforcing sheet and reached the surface of the above-mentioned polypropylene foam sheet and was firmly integrated with the polypropylene foam sheet.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the kenaf fibers comprising the above-mentioned reinforcing sheet (A2) were firmly bound together with the polyvinyl alcohol and the thermoplastic urethane resin as a binder. In addition, the kenaf fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet
  • An extruder used in the embodiment 1 was used to which a T die of 1600mm wide was attached instead of the adaptor for connecting the second extruder to the tip of the first extruder.
  • 1.0 weight parts of 1,9-nonanedioldimethacrylate as a crosslinking agent 10 weight parts of azodicarbonamide as a pyrolysis-type foaming agent, 0.1 weight parts of 2,6-di-t-butyl-p-crezol and 0.1 weight parts of dilauryl thiodipropionate as antioxidants, and 0.2 weight parts of methylbenzotriazol as a metal deactivator
  • Electron beam of 2 Mrad was applied to the obtained expandable polypropylene sheet at an acceleration voltage of 600kV in order to provide a crosslinking structure.
  • gel fraction of the expandable polypropylene sheet was 20 weight %.
  • the expandable multi-layer sheet which was obtained by ⁇ layering the above-mentioned laminated surface material on each of both surfaces of the above-mentioned expandable polypropylene sheet in a manner that the sheet for reinforcement came inside, was fed into the belt-type heating apparatus and was heated to 230°C in order to foam the expandable polypropylene sheet, and by having the above-mentioned laminated surface material pressed against each of both surfaces of the thermoplastic resin foam sheet, which was obtained by foaming the expandable polypropylene sheet, the former and the latter were integrated, which were then cooled in order to obtain the multi-layer sheet of 6.5mm thick comprising the reinforcing sheet and the surface layer layered on and integrated with the each of the both surfaces of the polypropylene foam sheet in this order in a manner that the reinforcing sheet came inside.
  • the reinforcing sheet (A1) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both surfaces of the polypropylene foam sheet.
  • the carbon fibers comprising the above-mentioned reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder.
  • the carbon fibers are in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer (A3) of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the above-mentioned belt-type heating apparatus comprises the preheating zone 1, the foaming zone 2, the cooling zone 3, and the pair of conveyer belts 4, 4 which are arranged extendedly over the three zones leaving a predetermined clearance in a up-and-down direction.
  • the expandable multi-layer sheet was placed on the upper surface of the lower conveyer belt of the pair of the conveyer belts 4,4, and was sent into the preheating zone 1, the foaming zone 2 and the cooling zone 3 in this order, so that the above-mentioned expandable multi-layer sheet was able to be foamed between the inner surfaces of the conveyer belts 4, 4 facing to each other, and while foaming of the above-mentioned expandable multi-layer sheet 5 was in progress, the expandable multi-layer sheet 5 was held and pressed from up-and-down directions between the inner surfaces of the conveyer belts 4, 4 facing to each other in order to press the sheet for reinforcement toward each of both sides of the expandable polypropylene sheet to make the former and the latter integrated together.
  • the multi-layer sheet was obtained in which the reinforcing sheet and the surface layer were layered in this order on each of both sides of the polypropylene foam sheet.
  • a temperature of the preheating zone was set to be 190°C
  • a temperature of the foaming zone was set to be 230°C
  • a temperature of the cooling zone was set to be 25°C
  • a linear velocity of feed of the expandable polypropylene sheet into the belt-type heating apparatus was set to be 0.5m/minute.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the glass fibers comprising the reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the glass fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the kenaf fibers comprising the reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the kenaf fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the multi-layer sheet was obtained in a similar manner as in the embodiment 8 except that as the surface film, the non-woven fabric, whose per-unit weight was 25g/m 2 , was used, which non-woven fabric comprises core-sheath type fibers interwound with one another, and which core-sheath type fiber comprises polyester as a core and polyethylene as a sheath.
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the carbon fibers comprising the reinforcing sheet (A2) were firmly bound together with polypropylene, being melted polypropylene fibers, as a binder. In addition, the carbon fibers were in a state of being covered and concealed with the above-mentioned surface layer (A3) and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces. In the meantime, the core-sheath type fibers were melted and shape and state of fibers completely disappeared to form a smooth surface layer (A3).
  • homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the glass fibers comprising the reinforcing sheet (A2) were firmly bound together with the acrylate-based emulsion resin as a binder. In addition, the glass fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • the homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the carbon fibers comprising the reinforcing sheet (A2) were firmly bound together with the acrylate-based emulsion resin as a binder. In addition, the carbon fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • the reinforcing sheet (A2) of the obtained multi-layer sheet (A) was firmly layered on and integrated with each of both sides of the polypropylene foam sheet (A1). And the kenaf fibers comprising the reinforcing sheet (A2) were firmly bound together with the polyvinyl alcohol and the thermoplastic urethane resin as a binder. In addition, the kenaf fibers were in a state of being covered and concealed with the above-mentioned surface layer and both surfaces of the multi-layer sheet (A) were formed to be smooth surfaces.
  • homo-type polypropylene comprising the surface layer of the above-mentioned multi-layer sheet (A) entered into the reinforcing sheet (A2), reached the surface of the above-mentioned polypropylene foam sheet (A1) and was firmly integrated with the polypropylene foam sheet (A1).
  • Per-unit strength, coefficient of linear expansion and handling efficiency of each multi-layer sheet obtained in the embodiments 1 to 14 and the example for comparison 1 an expansion ratio and an aspect ratio of each thermoplastic resin foam sheet of each multi-layer sheet, and a per-unit weight of each reinforcing sheet of each multi-layer sheet and a content of non-meltable fibers of each reinforcing sheet were determined in manners as mentioned below, and the results thereof are shown in Tables 1 and 2.
  • the female-type metal mold 6 comprises a plane-square-shaped female-type metal mold main body 61 in a center of an upper side of which a truncated-right-pyramid-shaped concavity 62 of 1500mm long ⁇ 1200mm wide ⁇ 300mm deep is formed. Both of each ridge and each edge of an opening of the concavity 62 are chamfered to form a circular arc.
  • a male-type metal mold main body 71 is formed to be plane square-shaped whose shape and size are the same as the above-mentioned female-type metal mold main body 62 of the female-type metal mold 6, and a truncated-right-pyramid-shaped convexity 72, which can fit the concavity 62 of the female-type metal mold 6, is formed to project in a center of a lower side of the male-type metal mold main body 71.
  • Polyester non-woven fabric 8 with a per-unit weight of 200g/m 2 was placed on an upper surface of the multi-layer sheet (A), the multi-layer sheet (A) was heated until a surface temperature of the multi-layer sheet (A) became 180°C and was arranged between the above-mentioned female-type metal mold 6 and the male-type metal mold 7. Next, the female-type metal mold 6 and the male-type metal mold 7 are clamped with a clearance of 5mm and the multi-layer sheet (A) was formed in-between under pressure in order to provide a molding product 9 in a shape as shown in Fig. 5.
  • the female-type metal mold 6 and the male-type metal mold 7 are regulated to be 40°C, and time for clamping of the female-type metal mold 6 and the male-type metal mold 7was 30 seconds. Further, after the female-type metal mold 6 and the male-type metal mold 7 were opened, the obtained molding product 9 was trimmed.
  • the molding product with neither crinkle nor crack on a surface thereof was marked o ⁇ the one with a little crinkles and cracks was marked ⁇ , and the one with a lot of crinkles and cracks was marked ⁇ .
  • the molding product 9 After sticking an iron plumb bob of 500g on a center part of the concavity 91 of the molding product 9, which was obtained in the above-mentioned manner, the molding product 9 was placed on a flat floor surface, was lifted upward to a predetermined height by holding center portions of rims of four sides of the molding product, and was placed on the floor surface again. This action was repeated 10 times and the one without any crinkle, dent and fold was marked ⁇ , the one with at least one of crinkle, dent and fold on at least a part was marked ⁇ .
  • Expansion ratio was determined according to Japanese Industrial Standard K6767.
  • a polypropylene foam sheet of the multi-layer sheet was cut in a direction of a thickness thereof, and an enlarged picture by 20 times of a center part of a section thereof was taken with an optical microscope.
  • an aspect ratio (Dz/Dxy) of each bubble which was an object of determination, was determined, and a mean value was calculated.
  • the bubbles with a life-size (Dz) of less than 0.1mm and the bubbles with the life-size (Dz) exceeding 2mm were not made to be objects of determination.
  • a specimen of 2cm wide ⁇ 5cm long was cut out of each of ten multi-layer sheets. Then the polypropylene foam sheet of each specimen was exfoliated and removed. The surface of the reinforcing sheet, which was left after exfoliation and removal of the polypropylene foam sheet, was rubbed with sandpaper in order to completely remove the above-mentioned thermoplastic resin foam sheet. Further, the surface layer, which was layered on and integrated with the surface of the above-mentioned reinforcing sheet, was scraped with a milling machine until the non-meltable fibers of the reinforcing sheet became exposed. A unit-weight of each reinforcing sheet obtained in this manner was determined, a mean value of the numbers was calculated to determine the per-unit weight of the reinforcing sheet.
  • the multi-layer sheet according to this invention has a structure as mentioned above, the multi-layer sheet is excellent in bending strength, compressive strength, thermoforming property and dimensional stability as well as lightweight property, and can ideally be used for an upholstery material for vehicles, an insulation material and a buffer material.
  • the above-mentioned multi-layer sheet can be obtained without fail in such a simple manner that after the sheet for reinforcement is layered on one side of the expandable sheet to provide the expandable multi-layer sheet, the expandable multi-layer is foamed by using the heating apparatus which is generally used.
  • the multi-layer sheet according to this invention is useful as an upholstery material for vehicles such as a ceiling material for vehicles, etc., an insulation material and further as a buffer material, and is particularly ideal for being used as a ceiling material for vehicles.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)
EP00905391A 2000-02-28 2000-02-28 Mehrschichtiges laminat, harstellungs- und formgebungsverfahren Withdrawn EP1270199A4 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2000/001152 WO2001064431A1 (fr) 2000-02-28 2000-02-28 Feuille laminee, procede de production de feuille laminee et procede de formage de feuille laminee

Publications (2)

Publication Number Publication Date
EP1270199A1 true EP1270199A1 (de) 2003-01-02
EP1270199A4 EP1270199A4 (de) 2003-07-02

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FR2890890A1 (fr) * 2005-09-22 2007-03-23 Faurecia Sieges Automobile Element accessoire de siege de vehicule automobile comportant un rembourrage de mousse synthetique, tel qu'un appui-tete, et procede de fabrication de cet element.
EP3218181B1 (de) 2014-11-10 2018-08-29 J.H. Ziegler GmbH Kaschierungstextilverbundmaterial enthaltend eine vliesstoffkomponente und eine schaumstoffkomponente
EP4253048A1 (de) * 2022-03-28 2023-10-04 Meiwa Industry Co., Ltd. Schichtplatte

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WO2011099611A1 (ja) * 2010-02-15 2011-08-18 倉敷紡績株式会社 繊維強化樹脂用シート及びこれを用いた繊維強化樹脂成形体
BR112015022947A2 (pt) 2013-03-15 2017-07-18 Miller Herman Inc componente de espuma de partículas possuindo uma superfície texturizada
CA2859114A1 (en) * 2013-08-29 2015-02-28 International Automotive Components Group North America, Inc. Formed articles comprising carbon and natural fibers, methods of manufacture and use thereof
US10059091B2 (en) * 2015-02-27 2018-08-28 Orbis Corporation Partition
DE102016222392B4 (de) * 2016-11-15 2021-04-08 Ideal Automotive Gmbh Verfahren zum Herstellen einer Verbundplatte, Verfahren zur Herstellung eines Verkleidungsteils, Verbundplatte und Verkleidungsteil
WO2020158600A1 (ja) * 2019-01-30 2020-08-06 株式会社Ｈｏｗａ 乗物用内外装材、乗物用内外装材の製造方法及び乗物用内外装材の製造に用いるプレス型
CN111890527B (zh) * 2020-08-05 2021-09-28 洛阳北玻硅巢新材料有限公司 一种通过棚板拼接模具烧制复合保温板的方法

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FR2890890A1 (fr) * 2005-09-22 2007-03-23 Faurecia Sieges Automobile Element accessoire de siege de vehicule automobile comportant un rembourrage de mousse synthetique, tel qu'un appui-tete, et procede de fabrication de cet element.
EP3218181B1 (de) 2014-11-10 2018-08-29 J.H. Ziegler GmbH Kaschierungstextilverbundmaterial enthaltend eine vliesstoffkomponente und eine schaumstoffkomponente
EP3218181B2 (de) † 2014-11-10 2023-01-04 J.H. Ziegler GmbH Kaschierungstextilverbundmaterial enthaltend eine vliesstoffkomponente und eine schaumstoffkomponente
EP4253048A1 (de) * 2022-03-28 2023-10-04 Meiwa Industry Co., Ltd. Schichtplatte

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US6984445B1 (en) 2006-01-10
EP1270199A4 (de) 2003-07-02

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